EP0527143B1 - Coated abrasive alumina particles, manufacture and use - Google Patents
Coated abrasive alumina particles, manufacture and use Download PDFInfo
- Publication number
- EP0527143B1 EP0527143B1 EP91907376A EP91907376A EP0527143B1 EP 0527143 B1 EP0527143 B1 EP 0527143B1 EP 91907376 A EP91907376 A EP 91907376A EP 91907376 A EP91907376 A EP 91907376A EP 0527143 B1 EP0527143 B1 EP 0527143B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- abrasive
- alumina
- coated
- abrasive particles
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000002245 particle Substances 0.000 title claims abstract description 76
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000011819 refractory material Substances 0.000 claims abstract description 19
- 238000000576 coating method Methods 0.000 claims description 54
- 229910052751 metal Inorganic materials 0.000 claims description 52
- 239000002184 metal Substances 0.000 claims description 52
- 239000011248 coating agent Substances 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 16
- 150000004767 nitrides Chemical class 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 229910052743 krypton Inorganic materials 0.000 claims description 3
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 14
- 239000011707 mineral Substances 0.000 abstract description 14
- 239000000919 ceramic Substances 0.000 abstract description 12
- 238000000541 cathodic arc deposition Methods 0.000 abstract description 11
- 238000000227 grinding Methods 0.000 description 35
- 239000006061 abrasive grain Substances 0.000 description 33
- 238000005520 cutting process Methods 0.000 description 22
- 239000000463 material Substances 0.000 description 20
- 239000010410 layer Substances 0.000 description 12
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 12
- 229910010271 silicon carbide Inorganic materials 0.000 description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 description 9
- 230000006872 improvement Effects 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000003082 abrasive agent Substances 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 230000004907 flux Effects 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 239000010432 diamond Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- -1 VIB metals Chemical class 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 4
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910003460 diamond Inorganic materials 0.000 description 4
- 150000001247 metal acetylides Chemical class 0.000 description 4
- 229920003987 resole Polymers 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 4
- 229910052582 BN Inorganic materials 0.000 description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 3
- 230000001464 adherent effect Effects 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000003870 refractory metal Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052580 B4C Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910026551 ZrC Inorganic materials 0.000 description 2
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 238000004924 electrostatic deposition Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000010297 mechanical methods and process Methods 0.000 description 2
- 230000005226 mechanical processes and functions Effects 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 2
- 229910017083 AlN Inorganic materials 0.000 description 1
- 229910017109 AlON Inorganic materials 0.000 description 1
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229910000760 Hardened steel Inorganic materials 0.000 description 1
- 229910020491 K2TiF6 Inorganic materials 0.000 description 1
- 229910020261 KBF4 Inorganic materials 0.000 description 1
- 241000233805 Phoenix Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- BGECDVWSWDRFSP-UHFFFAOYSA-N borazine Chemical compound B1NBNBN1 BGECDVWSWDRFSP-UHFFFAOYSA-N 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 229910001610 cryolite Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1436—Composite particles, e.g. coated particles
- C09K3/1445—Composite particles, e.g. coated particles the coating consisting exclusively of metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1436—Composite particles, e.g. coated particles
Definitions
- This invention relates to a method of producing abrasive particles by cathodic arc deposition of refractory material on alumina-based core particles, the abrasive particles produced by the method and abrasive articles made with the abrasive particles.
- Particulate aluminum oxide or alumina has long been employed as abrasive particles or grain in various abrasive products.
- the first source for alumina abrasive particles was the abundant supply which was found in nature.
- the naturally occurring alumina was later improved by fusion techniques, heat treatments and the addition of various additives. While such techniques have resulted in a dramatic improvement in the performance of abrasive articles which contain such abrasive particles, there still exists a great need for further improved alumina abrasive material to make it better able to withstand the reactivity and the abrasive wear caused by contact with a metal workpiece.
- U.S. Patent No. 4,366,254 describes a cutting tool of alumina, zirconia, and optionally a refractory metal compound such as a metal carbide, nitride, or carbo-nitride of the Group IVB and VB metals and the carbides of the Group VIB metals of the Periodic Table to provide a cutting tool which is tough without being as wear resistant as pure alumina.
- 4,543,343 describes a cutting tool comprising a high thermal conductivity ceramic material made of alumina, titanium boride, titanium carbide, and zirconia.
- U.S. Patent No. 4,776,863 describes a cutting tool of hard metal which is coated with hard layers of titanium carbide, titanium carbonitride and/or titanium nitride, with an outermost thin layer of zirconium nitride. Successive layers of titanium carbonitride are coated via chemical vapor deposition (CVD) methods as is the zirconium nitride layer which according to the patent can also be deposited via physical vapor deposition (PVD) methods. PVD methods include evaporation by sputtering or by arc evaporation.
- CVD chemical vapor deposition
- PVD physical vapor deposition
- a multilayer coated cemented carbide cutting tool is disclosed in U.S. Patent No. 4,746,563.
- This patent describes the use of CVD methods to form successive layers of alumina and metal nitrides or carbides on a cemented carbide substrate.
- the alumina layer with a total thickness ranging from 5 to 20 micrometers is divided into a plurality of layers each having a thickness ranging from 0.01 to 2 micrometers (10 to 2000 nanometers) by use of interlayers each of which has a thickness of 0.01 to 2 micrometers and consists of at least one member selected from the group consisting of TiC, TiN, TiCN, TiCNO, TiCO, TiNO, Ti oxides, Ti(B,N), Ti(B,N,C), SiC, AlN, and AlON.
- Sputtering with a coating metal such as molybdenum has been used to coat diamond with an adherent metal layer to promote the bonding between diamond particles when formed into a compact, as described in U.S. Patent No. 3,351,543.
- the cited advantage was to be able to bond together small synthetically made diamonds of variable sizes into a usable tool. Sputtering was used to clean the surface of the diamonds and then to coat with molybdenum. Coating thickness are reported as ranging from about 58 nanometers to 200 nanometers.
- Cutting tools cannot be equated with abrasive grain for several reasons. Grinding was once considered to be a purely mechanical action of metal removal much as a cutting tool. This was supported by the fact that the two commonly used abrasives, alumina and silicon carbide (SiC), behaved differently on different materials. Alumina, believed to be the harder mineral, was effective on high tensile steels while SiC was more effective on low tensile materials. With further study of these materials, it was determined that SiC was actually the harder of the two minerals. With the development of B4C, which was a much harder than either alumina or SiC, it was found that this new mineral was inferior to both alumina and SiC in grinding steels. The theory that grinding was totally a mechanical process fell apart.
- U.S. Patent No. 4,788,167 is an example of the former.
- an abrasive grain comprising aluminum nitride, aluminum oxynitride, and Periodic Group IVB metal nitride.
- the compositions described offer improvement over known compositions in grinding cold-rolled steel.
- Patent Publication JP1-113485 published May 2, 1989, which describes alumina, zirconia, or silicon carbide abrasive grain coated with diamond or cubic boron nitride via chemical vapor deposition processes for use in grinding wheels, cutting blades, and finishing work.
- This publication is directed to conversion of the abrasive grains to "superhard” grains by coating them with diamond or boron nitride in thicknesses ranging from 0.5 to 10 micrometers (500 to 10000 nanometers).
- U.S. Patent No. 4,505,720 assigned to the assignee of the present application, describes an improved granular abrasive mineral made by coating hard refractory material onto silicon carbide abrasive grain. The coatings are applied by chemical vapor deposition onto silicon carbide grit in a fluidized bed. The resultant coated grain offers a significant increase in abrasive performance when used to grind steel.
- Metal capping is the term used to describe the coating of abrasive particles by metal from a workpiece during abrading. Metal capping dramatically reduces the effectiveness of a coated abrasive product. It is a particularly bothersome problem when fine-grade abrasive particles ( ⁇ 100 mesh or 150 micrometers in average particle size) are used. It is believed that elimination or reduction of the metal caps would improve the grinding rate and increase the useful life of the abrasive mineral.
- the present invention provides alumina-based abrasive particles coated with an adherent thin (less than 0.1 micrometer) layer of metal boride, carbide or nitride refractory material which, when incorporated into an abrasive product such as a coated abrasive disc, provides notable improved abrasive performance.
- this improved abrasive performance is believed to be due to the formation of an interface or barrier layer which prevents the metal workpiece from reacting with the surface of the abrasive particles while at the same time maintaining its abrasive characteristics.
- This barrier is provided by coating the alumina-based abrasive particles with refractory metal nitride, carbide, and boride via cathodic arc deposition.
- the abrasive particles of the invention are characterized by each particle comprising an alumina-based core coated with a substantially uniform layer of refractory material at an average coating thickness of less than 100 nanometers.
- the coatings are preferably a refractory material which is selected from the group of metal borides, carbides, and nitrides.
- Preferred metal borides, carbides, and nitrides are of a metal selected from the group consisting of scandium, lanthanum, cerium, neodymium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten and mixtures thereof. Boron carbides and nitrides are also useful.
- the preferred coating thickness on the order of 1 to 100 nanometers, preferably 5 to 25 nanometers.
- the alumina-based core of the abrasive particles of the present invention is preferably fused alumina, fused alumina:zirconia, or a alumina-based ceramic material such as that obtained by a sol gel process.
- the preferred ceramics are alpha-alumina based ceramic materials which are made by a sol gel process which may be seeded to provide a finer domain structure or modified to provide a more durable grain with a modifier such as magnesia which on firing the ceramic will produce an alumina:magnesia spinel.
- the abrasive particles of the present invention are made by a process which comprises:
- the atmosphere may comprise an inert gas such as argon, krypton, xenon, helium, or a member of Group 8 of the Periodic Table and a reactive gas, or a reactive gas alone.
- Suitable reactive gases include oxygen, nitrogen, ammonia, a hydrocarbon, or a boron-containing gas.
- the present invention also provides abrasive articles which comprise abrasive grains which may be substituted partly or in whole by the abrasive particles of the present invention.
- abrasive articles are coated abrasive products (commonly called sandpaper), bonded abrasive products (e.g., grinding wheels or honing stones), or nonwoven abrasive products.
- Such products are conventional except the substitution of all or part of the conventional abrasive particles with the abrasive particles of the present invention.
- Coated abrasive discs made with the abrasive grains of the present invention show improved grinding performance over the same abrasive discs containing conventional alumina-based abrasive particles without the refractory coating on various metal workpieces such as stainless steel and mild steel.
- the useful life of the abrasive discs of the present invention is noted to be considerably extended because of the presence of the refractory coating on the abrasive particles. It is thought that the extended life is indicative of a reduction of the metal capping problem. It is expected that the grinding performance of other metal workpieces such titanium, hardened steel, metal alloys would likewise be improved by use of abrasive products which contain abrasive particles according to the present invention.
- the preferred alumina-based particles which are coated with the refractory materials according to the present invention include fused alumina, fused alumina-zirconia, and sol gel derived ceramic alpha alumina-based abrasive particles with and without seeding materials or modifiers.
- the alumina-based abrasive particles are preferably made via a sol gel process. Examples of such abrasive grains may be found in the disclosures of U.S. Patent Nos. 4,314,827; 4,744,802; 4,770,671; and 4,881,951.
- a cathodic arc deposition process is used to coat a refractory material over an alumina-based abrasive particle.
- the alumina-based abrasive particles are placed in a vacuum chamber of a cathodic arc deposition device in or on a device which agitates or vibrates the particles to obtain uniform surface coating in a directional plasma field.
- Illustrative examples of methods for agitating the abrasive particles include shaking, vibrating, or rotating the reactor, stirring the particles or suspending them in a fluidized bed.
- a preferred reaction chamber is comprised of a cylinder fitted with baffles which stir the particles during the coating process.
- the particles may be agitated by many different ways such that essentially the entire surface of each particle is exposed to the coating flux. Agitation of the particles also tends to prevent agglomeration and to achieve uniform mixing, which results in more uniform coating.
- the chamber is evacuated and then backfilled with inert and/or reactive gases to a desired operating pressure.
- a high current is applied and maintained at the source cathode during the deposition.
- Reactive deposition of compounds is possible in cathodic arc coating by the simple addition of reactive gas into the coating chamber.
- An anode and cathode are provided and placed in such an orientation that when an arc discharge is initiated and when current of sufficient magnitude is supplied to the cathode, an arc discharge occurs between the anode and cathode.
- the arcs formed are small luminous regions which are very mobile and move rapidly over the cathode surface. Due to the high current density in each spot, rapid ebullition of the cathode material occurs as soon as current is supplied to the cathode.
- the resulting plasma or beam of particles consists of atoms and ions of source (cathode) material and each particle has a kinetic energy between about 10 and 100 electron volts.
- a magnetic solenoid directs the beams of atoms and ions onto the substrate surface. The atoms and ions are generally considered to react at the substrate surface with the reactive gases in the chamber to form a thin film.
- the coating process typically requires about 5 hours of run time, although from between 1 to 10 hours might also be used.
- the refractory coated abrasive particles are removed from the vacuum chamber at the end of the run time, and then are used to make abrasive articles.
- an inert gas it is more typical not to use inert gas.
- the capability of backfilling with inert gases is sometimes desirable because it helps stabilize the discharge from the cathode.
- an inert gas it may be selected from argon, krypton, xenon, helium and any other gas which is chemically inert in a plasma environment. Argon is generally preferred due to cost and availability.
- Reactive gases which can be used to form compounds by this method include oxygen, nitrogen, ammonia, hydrocarbons, and boron-containing gases such as diborane and borazine.
- Metals useful in forming the nitride, carbide, or boride coatings in the present invention include, for example, scandium, lanthanum, cerium, neodymium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten and mixtures thereof.
- the coating is applied at a thickness of about 1 to 100 nanometers.
- High energy plasma from the cathodic arc process tends to encourage the formation of stoichiometric coatings. Because of the high energies involved in the coating process, the coatings are typically very adherent to the substrate.
- coated abrasive particles according to the present invention may be utilized in conventional abrasive products, in some instances it may be preferable that they be used as a blend with less expensive conventional abrasive grits such as fused alumina, silicon carbide, garnet, fused alumina-zirconia and the like. They may also be blended with minerals or materials which are not noted as abrasives such as calcium carbonate, glass, and the like.
- abrasive particles of the present invention may be blended with less expensive abrasive minerals.
- Such blending of abrasive particles is known.
- a preferred method of blending is described in assignee's U.S. Pat. No. 4,734,104 involving a method known as selective mineral substitution wherein the coarse abrasive mineral is removed from an inexpensive abrasive particle charge that is to be utilized in an abrasive product such as a coated abrasive and is substituted with coarse mineral of the invention.
- the improved abrasive particles of the present invention would be interposed in an abrasive product between smaller abrasive particles of conventional abrasive mineral to permit the improved coarse abrasive particles to do the bulk of the abrading with such product.
- a coated abrasive product includes a backing, for example, formed of fabric (e.g., woven or non-woven fabric such as paper) which may be saturated with a filled binder material, a polymer film such as that formed of oriented heat-set polypropylene or polyethylene terephthalate which may be first primed, if needed, with a priming material, or any other conventional backing material.
- the coated abrasive also includes a binder material, typically in layers including a make or maker coat, a size or sizing coat and possibly a supersize coat. Conventional binder materials include phenolic resins.
- Grinding aids may also be added to the size coat or as particulate material.
- the preferred grinding aid is KBF4, although other grinding aids are also believed to be useful.
- Other useful grinding aids include NaCl, sulfur, K2TiF6, polyvinyl chloride, polyvinylidene chloride, cryolite and combinations and mixtures thereof.
- the preferred amount of grinding aid is on the order of 50 to 300 g., preferably 80 to 160 g. per square meter of coated abrasive product.
- Non-woven abrasive products typically include an open porous lofty polymer filament structure having the refractory coated alumina abrasive grits distributed throughout the structure and adherently bonded therein by an adhesive material.
- the method of making such non-woven abrasive products is well known.
- Bonded abrasive products typically consist of a shaped mass of abrasive grits held together by an organic or ceramic binder material.
- the shaped mass is preferably in the form of a grinding wheel.
- the preferred binder materials for the refractory coated alumina abrasive grits of the invention are organic binders. Ceramic or vitrified binders may be used if they are curable at temperatures and under conditions which will not adversely affect the abrasive grits of the present invention.
- alumina-based abrasive particles are weighed out and placed in a holder in a vacuum system.
- the holder is positioned to receive the maximum coating flux using a Model 1000 boron nitride confined-type cathodic arc apparatus which is commercially available from Metco Cat Arc division of the Perkin Elmer Corp. This apparatus is similar to that described in U.S. Patent No. 3,836,451 (Snaper).
- the apparatus is further equipped with a magnetic solenoid as described in Gilmore et al., "Pulsed Metallic-Plasma Generators," Proceeding of the IEEE , V. 60, No. 8, pp. 977-991.
- the holder is positioned about 7.6 cm from the cathode.
- the zirconium and titanium cathodes used are commercially available and are obtained from Phoenix Metallurgical Corporation, Houston, Texas, having 7.62 cm diameter and 2.5 cm thickness.
- the cathode is mounted on a water-cooled cathode holder, which is installed in a vacuum chamber of the apparatus. After the vacuum chamber is evacuated to 5 x 10 ⁇ 6 torr, the high vacuum diffusion pump is throttled, and argon and a reactive gas, or reactive gas alone is admitted to the chamber at a flow rate sufficient to maintain 10 - 20 millitorr pressure in the chamber. Typically the gas flow rates are adjusted throughout a run in order to maintain a constant pressure. An arc is ignited on the cathode surface and is regulated by a constant current power supply to 150 amps for 400 gram abrasive grain charge runs, and 180 amps for 2000 gram charge runs.
- a solenoid providing a magnetic field of about 50 Gauss serves to duct the titanium or zirconium plasma to the abrasive grain while agitating the abrasive grain in a cylinder fitted with baffles which stir the grain during the coating process.
- a typical coating run time is about 5 hours.
- the grain is first conventionally coated on a backing and then converted into 7.6 cm x 335 cm grinding belts. Grinding tests are carried out on a constant load surface grinder.
- the workpiece is then reciprocated vertically through an 18 cm path at the rate of 20 cycles per minute, while a spring loaded plunger urges the workpiece against the belt under a load of 11.36 Kg as the belt is driven at about 2050 meters per minute.
- the test is run by grinding the preweighed workpiece for 1 minute, reweighing the workpiece to obtain the weight of metal removed, and then cooling the workpiece. Successive workpieces were treated the same way until the workpiece set has been completed and then the cycle is repeated until the desired endpoint is obtained.
- the amount of stock removed is calculated by adding the amount of metal removed from each workpiece for each minute of grinding to obtain a total weight of metal removed.
- HTA heat treated fused alumina
- Grade 150 average particle size of about 95 micrometers
- the grit was exposed to the coating flux for 5 hours, sufficient to yield a coating thickness of approximately 10 nanometers, as calculated.
- the average coating thickness was calculated from the weight percent of the coating (as determined by standard analytical chemistry methods), the average surface area of the abrasive grain, and the density of the coating material (e.g., titanium nitride has a density of 5.22 g/cc) using the following equation: where
- the coated abrasive grain was made into a coated abrasive product using conventional techniques.
- the coated abrasive product was converted into abrasive belts.
- Uncoated HTA was used to make a control coated abrasive which was also converted to an abrasive belt.
- the backing material was a Y weight sateen polyester and the belt size was 7.6 cm x 335.3 cm.
- the backing was coated with a traditional CaC03 filled phenol formaldehyde resole resin make coat which, upon curing, contained 45.2% CaC03 and 54.8% resin. Then abrasive mineral was applied by electrostatic deposition. The make coat was precured for 2 hours at 80°C and then a size coat was applied.
- the size coat was a traditional CaC03 filled phenolic resole resin which, upon curing, contained 59.6% CaC03 and 40.4% resin. After application of the size coat coated abrasive was cured for 12 hours at 100°C.
- HTA heat treated fused alumina
- the abrasive grain was exposed to the coating flux for 5 hours, sufficient to yield a coating thickness of approximately 10 nanometers.
- the resulting coated abrasive grain was used to make coated abrasives which were converted into belts and tested as described in Example 1, with results as follows: Total Amount of Metal Removed by Control Belt: 352.3 grams Total Amount of Metal Removed by Example 2 Belt: 390.6 grams Percent Improvement: 10.8%
- the abrasive was exposed to the coating flux for 5 hours, sufficient to yield a calculated coating thickness of approximately 10 nanometers.
- the resulting coated abrasive grain was used to make coated abrasive product which was converted into abrasive belts and tested as described in Example 1, with results as follows: Total Amount of Metal Removed by Control Belt: 248.3 grams Total Amount of Metal Removed by Example 3 Belt: 268.26 grams Percent Improvement: 8.2%
- the abrasive grain was exposed to the coating flux for 5 hours, sufficient to yield a calculated coating thickness of approximately 10 nanometers.
- the resulting coated abrasive grain was used to make coated abrasive using conventional techniques and the coated abrasive was converted into abrasive belts. Uncoated Cubitron grain was used to make coated abrasive which was converted to a control belt.
- the coated abrasive backing material was a treated cotton J weight drill cloth, obtained from Gustav Ernstmeier Gmbh and Co. KG, West Germany, and the belt size was 7.6 cm x 335.3 cm.
- the cloth was coated with a traditional CaC03 filled phenolic resole resin which, upon curing, resulted in a solids content of 42% CaC03 and 58% resin. Then abrasive mineral was applied by electrostatic deposition to a density of 0.0151 gram/cm2.
- the make coat was precured according to the following heating schedule: 4 minutes @ 71°C 20 minutes @ 96°C 74 minutes @ 104°C
- the size coat was a traditional CaC03 filled phenolic resole resin which, upon curing, had a solids content of 80% CaC03 and 20% resin.
- the belt was cured according the following heating schedule: 20 minutes @ 57°C 40 minutes @ 71°C 20 minutes @ 81°C 80 minutes @ 89°C 90 minutes @ 58°C
- the grit was exposed to the coating flux for 5 hours, sufficient to yield a calculated coating thickness of approximately 10 nanometers.
- the coated abrasive grain was used to make coated abrasive product which was converted into abrasive belts and tested as described in Example 4, with results as follows: Total Metal Removed by Control Belt: 304.9 grams Total Metal Removed by Example 5 Belt: 395.1 grams Percent Improvement: 29.6%
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Abstract
Description
- This invention relates to a method of producing abrasive particles by cathodic arc deposition of refractory material on alumina-based core particles, the abrasive particles produced by the method and abrasive articles made with the abrasive particles.
- Particulate aluminum oxide or alumina has long been employed as abrasive particles or grain in various abrasive products. The first source for alumina abrasive particles was the abundant supply which was found in nature. The naturally occurring alumina was later improved by fusion techniques, heat treatments and the addition of various additives. While such techniques have resulted in a dramatic improvement in the performance of abrasive articles which contain such abrasive particles, there still exists a great need for further improved alumina abrasive material to make it better able to withstand the reactivity and the abrasive wear caused by contact with a metal workpiece.
- One with a limited amount of technical know-how, but not skilled in either the abrasive art or the ceramic cutting tool art, might look to the ceramic cutting tool art for guidance as to how abrasive particles may be improved to give them less reactivity and improved durability. For example, U.S. Patent No. 4,366,254 describes a cutting tool of alumina, zirconia, and optionally a refractory metal compound such as a metal carbide, nitride, or carbo-nitride of the Group IVB and VB metals and the carbides of the Group VIB metals of the Periodic Table to provide a cutting tool which is tough without being as wear resistant as pure alumina. U.S. Patent No. 4,543,343 describes a cutting tool comprising a high thermal conductivity ceramic material made of alumina, titanium boride, titanium carbide, and zirconia. U.S. Patent No. 4,776,863 describes a cutting tool of hard metal which is coated with hard layers of titanium carbide, titanium carbonitride and/or titanium nitride, with an outermost thin layer of zirconium nitride. Successive layers of titanium carbonitride are coated via chemical vapor deposition (CVD) methods as is the zirconium nitride layer which according to the patent can also be deposited via physical vapor deposition (PVD) methods. PVD methods include evaporation by sputtering or by arc evaporation.
- A multilayer coated cemented carbide cutting tool is disclosed in U.S. Patent No. 4,746,563. This patent describes the use of CVD methods to form successive layers of alumina and metal nitrides or carbides on a cemented carbide substrate. The alumina layer with a total thickness ranging from 5 to 20 micrometers is divided into a plurality of layers each having a thickness ranging from 0.01 to 2 micrometers (10 to 2000 nanometers) by use of interlayers each of which has a thickness of 0.01 to 2 micrometers and consists of at least one member selected from the group consisting of TiC, TiN, TiCN, TiCNO, TiCO, TiNO, Ti oxides, Ti(B,N), Ti(B,N,C), SiC, AlN, and AlON.
- Sputtering with a coating metal such as molybdenum has been used to coat diamond with an adherent metal layer to promote the bonding between diamond particles when formed into a compact, as described in U.S. Patent No. 3,351,543. The cited advantage was to be able to bond together small synthetically made diamonds of variable sizes into a usable tool. Sputtering was used to clean the surface of the diamonds and then to coat with molybdenum. Coating thickness are reported as ranging from about 58 nanometers to 200 nanometers.
- While certain of the aforementioned references indicate that improved physical properties may be obtained in ceramic cutting tools by the coating of such ceramic tools with refractory metal compounds, such disclosure does not direct the person skilled in the abrasive art to make similar modifications of alumina abrasive particles or grains.
- Cutting tools cannot be equated with abrasive grain for several reasons. Grinding was once considered to be a purely mechanical action of metal removal much as a cutting tool. This was supported by the fact that the two commonly used abrasives, alumina and silicon carbide (SiC), behaved differently on different materials. Alumina, believed to be the harder mineral, was effective on high tensile steels while SiC was more effective on low tensile materials. With further study of these materials, it was determined that SiC was actually the harder of the two minerals. With the development of B₄C, which was a much harder than either alumina or SiC, it was found that this new mineral was inferior to both alumina and SiC in grinding steels. The theory that grinding was totally a mechanical process fell apart.
- The reason why grinding is not totally a mechanical process may be found in comparing the distribution of energy used in metal removal by cutting tools and abrasive grinding. In cutting tools it has been estimated that up to 90% of the total energy used for cutting is removed with the chips and that only about 5% of this total energy goes into the metal surface as heat. As a result, the cutting tool temperature remains relatively low, about 700° to 800°C. for normal cutting speeds. For abrasive grinding, the total energy input into the operation is up to ten times greater than with cutting tools. And of the total energy input, about 80% goes into the workpiece at the grinding interface as heat compared with 5% for cutting tools. The energy going into the workpiece as heat is thus 160 times greater in the case of abrasive grinding than cutting tools. The reason for this difference may be found in the different mechanisms of chip formation and the values of rake angle. In cutting tools the rake angle is near zero allowing almost complete freedom for upward flow and removal of the chip. In abrasive grinding, rake angles have large negative values and there is considerable resistance to upward flow. As a result, considerable energy is spent in deforming the surface in grinding while little energy is removed with the chips. The temperature of the grinding interface thus reaches very high values, and may even reach the melting point of the metal as evidenced by solidified chips often found in the grinding swarf. Another indication of the high temperatures present is the spark shower observed in grinding which consists of chips heated to red or white heat.
- As a result of the high temperatures encountered at the grinding interface, the interaction between the metal, the abrasive grain and the atmosphere must be considered. For example, the best explanation of why aluminum oxide is a better abrasive on most steels than silicon carbide is that a chemical reaction occurs at the high temperatures encountered in abrasive grinding between the silicon carbide and the steel which in effect "melts" the abrasive and causes excessive wear. Tungsten carbide, boron carbide and titanium carbide are also examples of very hard materials which have been found to be excellent cutting tool materials, yet have little utility as an abrasive grain due to their reactivities with various metals.
- Thus, attempts at improving the grinding performance of abrasive grain for use in abrasive products such as coated abrasives generally have been directed away from substituting the bulk materials used in cutting tools for abrasive grain, and instead have focused on either changing the composition of the grain or on applying thin coats of refractory material to the grain.
- U.S. Patent No. 4,788,167 is an example of the former. In this patent, there is disclosed an abrasive grain comprising aluminum nitride, aluminum oxynitride, and Periodic Group IVB metal nitride. The compositions described offer improvement over known compositions in grinding cold-rolled steel.
- An example of the latter for various types of abrasive constructions is disclosed in laid open Patent Publication JP1-113485, published May 2, 1989, which describes alumina, zirconia, or silicon carbide abrasive grain coated with diamond or cubic boron nitride via chemical vapor deposition processes for use in grinding wheels, cutting blades, and finishing work. This publication is directed to conversion of the abrasive grains to "superhard" grains by coating them with diamond or boron nitride in thicknesses ranging from 0.5 to 10 micrometers (500 to 10000 nanometers).
- U.S. Patent No. 4,505,720, assigned to the assignee of the present application, describes an improved granular abrasive mineral made by coating hard refractory material onto silicon carbide abrasive grain. The coatings are applied by chemical vapor deposition onto silicon carbide grit in a fluidized bed. The resultant coated grain offers a significant increase in abrasive performance when used to grind steel.
- What has been lacking in the art, however, is an improvement in the grinding characteristics of alumina-based abrasive grain for use in coated abrasives to grind metal.
- One reason metal removal by alumina-based coated abrasives is generally at a low rate is probably due to "metal capping" of the abrasive particles. "Metal capping" is the term used to describe the coating of abrasive particles by metal from a workpiece during abrading. Metal capping dramatically reduces the effectiveness of a coated abrasive product. It is a particularly bothersome problem when fine-grade abrasive particles (<100 mesh or 150 micrometers in average particle size) are used. It is believed that elimination or reduction of the metal caps would improve the grinding rate and increase the useful life of the abrasive mineral.
- The present invention provides alumina-based abrasive particles coated with an adherent thin (less than 0.1 micrometer) layer of metal boride, carbide or nitride refractory material which, when incorporated into an abrasive product such as a coated abrasive disc, provides notable improved abrasive performance.
- While not being bound by theory, this improved abrasive performance is believed to be due to the formation of an interface or barrier layer which prevents the metal workpiece from reacting with the surface of the abrasive particles while at the same time maintaining its abrasive characteristics. This barrier is provided by coating the alumina-based abrasive particles with refractory metal nitride, carbide, and boride via cathodic arc deposition.
- Briefly, the abrasive particles of the invention are characterized by each particle comprising an alumina-based core coated with a substantially uniform layer of refractory material at an average coating thickness of less than 100 nanometers. The coatings are preferably a refractory material which is selected from the group of metal borides, carbides, and nitrides. Preferred metal borides, carbides, and nitrides are of a metal selected from the group consisting of scandium, lanthanum, cerium, neodymium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten and mixtures thereof. Boron carbides and nitrides are also useful.
- The preferred coating thickness on the order of 1 to 100 nanometers, preferably 5 to 25 nanometers.
- The alumina-based core of the abrasive particles of the present invention is preferably fused alumina, fused alumina:zirconia, or a alumina-based ceramic material such as that obtained by a sol gel process. The preferred ceramics are alpha-alumina based ceramic materials which are made by a sol gel process which may be seeded to provide a finer domain structure or modified to provide a more durable grain with a modifier such as magnesia which on firing the ceramic will produce an alumina:magnesia spinel.
- The abrasive particles of the present invention are made by a process which comprises:
- a) supplying sufficient current to a metal cathode to form a plasma of the metal comprising the cathode;
- b)subjecting the plasma to an atmosphere conducive to the formation of the boride, carbide, or nitride of the metal of the plasma;
- c) permitting the plasma to be directed in a path through an anode;
- d) maintaining alumina-based particles to be coated within the path;
- e) rotating each alumina-based particle to substantially expose the entire surface of each particle to the plasma path;
- f) continuing steps a-e until a substantially uniform coating of refractory material is coated on substantially every alumina particle; and
- g) discontinuing steps a-f before the average coating thickness of the refractory material on the alumina particle reaches 100 nanometers.
- The atmosphere may comprise an inert gas such as argon, krypton, xenon, helium, or a member of Group 8 of the Periodic Table and a reactive gas, or a reactive gas alone. Suitable reactive gases include oxygen, nitrogen, ammonia, a hydrocarbon, or a boron-containing gas.
- The present invention also provides abrasive articles which comprise abrasive grains which may be substituted partly or in whole by the abrasive particles of the present invention. Such abrasive articles are coated abrasive products (commonly called sandpaper), bonded abrasive products (e.g., grinding wheels or honing stones), or nonwoven abrasive products. Such products are conventional except the substitution of all or part of the conventional abrasive particles with the abrasive particles of the present invention.
- Coated abrasive discs made with the abrasive grains of the present invention show improved grinding performance over the same abrasive discs containing conventional alumina-based abrasive particles without the refractory coating on various metal workpieces such as stainless steel and mild steel. The useful life of the abrasive discs of the present invention is noted to be considerably extended because of the presence of the refractory coating on the abrasive particles. It is thought that the extended life is indicative of a reduction of the metal capping problem. It is expected that the grinding performance of other metal workpieces such titanium, hardened steel, metal alloys would likewise be improved by use of abrasive products which contain abrasive particles according to the present invention.
- The preferred alumina-based particles which are coated with the refractory materials according to the present invention include fused alumina, fused alumina-zirconia, and sol gel derived ceramic alpha alumina-based abrasive particles with and without seeding materials or modifiers. The alumina-based abrasive particles are preferably made via a sol gel process. Examples of such abrasive grains may be found in the disclosures of U.S. Patent Nos. 4,314,827; 4,744,802; 4,770,671; and 4,881,951.
- To produce abrasive particles according to the invention, a cathodic arc deposition process is used to coat a refractory material over an alumina-based abrasive particle. The alumina-based abrasive particles are placed in a vacuum chamber of a cathodic arc deposition device in or on a device which agitates or vibrates the particles to obtain uniform surface coating in a directional plasma field.
- Illustrative examples of methods for agitating the abrasive particles include shaking, vibrating, or rotating the reactor, stirring the particles or suspending them in a fluidized bed. A preferred reaction chamber is comprised of a cylinder fitted with baffles which stir the particles during the coating process. In such reaction chambers, the particles may be agitated by many different ways such that essentially the entire surface of each particle is exposed to the coating flux. Agitation of the particles also tends to prevent agglomeration and to achieve uniform mixing, which results in more uniform coating.
- The chamber is evacuated and then backfilled with inert and/or reactive gases to a desired operating pressure. A high current is applied and maintained at the source cathode during the deposition. Reactive deposition of compounds is possible in cathodic arc coating by the simple addition of reactive gas into the coating chamber.
- An anode and cathode are provided and placed in such an orientation that when an arc discharge is initiated and when current of sufficient magnitude is supplied to the cathode, an arc discharge occurs between the anode and cathode. The arcs formed are small luminous regions which are very mobile and move rapidly over the cathode surface. Due to the high current density in each spot, rapid ebullition of the cathode material occurs as soon as current is supplied to the cathode. The resulting plasma or beam of particles consists of atoms and ions of source (cathode) material and each particle has a kinetic energy between about 10 and 100 electron volts. A magnetic solenoid directs the beams of atoms and ions onto the substrate surface. The atoms and ions are generally considered to react at the substrate surface with the reactive gases in the chamber to form a thin film.
- The coating process typically requires about 5 hours of run time, although from between 1 to 10 hours might also be used. The refractory coated abrasive particles are removed from the vacuum chamber at the end of the run time, and then are used to make abrasive articles.
- It is common in vacuum deposition processes to use an inert gas to backfill the vacuum chamber. In the coating process of this invention, however, it is more typical not to use inert gas. The capability of backfilling with inert gases is sometimes desirable because it helps stabilize the discharge from the cathode. If an inert gas is used in the coating process, it may be selected from argon, krypton, xenon, helium and any other gas which is chemically inert in a plasma environment. Argon is generally preferred due to cost and availability.
- Reactive gases which can be used to form compounds by this method include oxygen, nitrogen, ammonia, hydrocarbons, and boron-containing gases such as diborane and borazine.
- Metals useful in forming the nitride, carbide, or boride coatings in the present invention include, for example, scandium, lanthanum, cerium, neodymium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten and mixtures thereof. The coating is applied at a thickness of about 1 to 100 nanometers.
- High energy plasma from the cathodic arc process tends to encourage the formation of stoichiometric coatings. Because of the high energies involved in the coating process, the coatings are typically very adherent to the substrate.
- The coated abrasive particles according to the present invention may be utilized in conventional abrasive products, in some instances it may be preferable that they be used as a blend with less expensive conventional abrasive grits such as fused alumina, silicon carbide, garnet, fused alumina-zirconia and the like. They may also be blended with minerals or materials which are not noted as abrasives such as calcium carbonate, glass, and the like.
- Because of the relatively high cost of coating the abrasive particles with refractory materials, it may be preferable to blend the abrasive particles of the present invention with less expensive abrasive minerals. Such blending of abrasive particles is known. A preferred method of blending is described in assignee's U.S. Pat. No. 4,734,104 involving a method known as selective mineral substitution wherein the coarse abrasive mineral is removed from an inexpensive abrasive particle charge that is to be utilized in an abrasive product such as a coated abrasive and is substituted with coarse mineral of the invention. It is recognized in that patent that in any coated abrasive the coarse abrasive grits are substantially responsible for a major portion of the abrading of a workpiece. By such substitution, the improved abrasive particles of the present invention would be interposed in an abrasive product between smaller abrasive particles of conventional abrasive mineral to permit the improved coarse abrasive particles to do the bulk of the abrading with such product.
- The coated abrasive particles of the present invention are conveniently handled and incorporated into various abrasive products according to well-known techniques to make, for example, coated abrasive products, bonded abrasive products, and lofty non-woven abrasive products. The methods of making such abrasive products are well-known to those skilled in the art. A coated abrasive product includes a backing, for example, formed of fabric (e.g., woven or non-woven fabric such as paper) which may be saturated with a filled binder material, a polymer film such as that formed of oriented heat-set polypropylene or polyethylene terephthalate which may be first primed, if needed, with a priming material, or any other conventional backing material. The coated abrasive also includes a binder material, typically in layers including a make or maker coat, a size or sizing coat and possibly a supersize coat. Conventional binder materials include phenolic resins.
- Grinding aids may also be added to the size coat or as particulate material. The preferred grinding aid is KBF₄, although other grinding aids are also believed to be useful. Other useful grinding aids include NaCl, sulfur, K₂TiF₆, polyvinyl chloride, polyvinylidene chloride, cryolite and combinations and mixtures thereof. The preferred amount of grinding aid is on the order of 50 to 300 g., preferably 80 to 160 g. per square meter of coated abrasive product.
- Non-woven abrasive products typically include an open porous lofty polymer filament structure having the refractory coated alumina abrasive grits distributed throughout the structure and adherently bonded therein by an adhesive material. The method of making such non-woven abrasive products is well known.
- Bonded abrasive products typically consist of a shaped mass of abrasive grits held together by an organic or ceramic binder material. The shaped mass is preferably in the form of a grinding wheel. The preferred binder materials for the refractory coated alumina abrasive grits of the invention are organic binders. Ceramic or vitrified binders may be used if they are curable at temperatures and under conditions which will not adversely affect the abrasive grits of the present invention.
- The following examples illustrate the present invention. All parts and percentages are by weight unless otherwise stated.
- For cathodic arc deposition, alumina-based abrasive particles are weighed out and placed in a holder in a vacuum system. The holder is positioned to receive the maximum coating flux using a Model 1000 boron nitride confined-type cathodic arc apparatus which is commercially available from Metco Cat Arc division of the Perkin Elmer Corp. This apparatus is similar to that described in U.S. Patent No. 3,836,451 (Snaper). The apparatus is further equipped with a magnetic solenoid as described in Gilmore et al., "Pulsed Metallic-Plasma Generators," Proceeding of the IEEE, V. 60, No. 8, pp. 977-991. The holder is positioned about 7.6 cm from the cathode. The zirconium and titanium cathodes used are commercially available and are obtained from Phoenix Metallurgical Corporation, Houston, Texas, having 7.62 cm diameter and 2.5 cm thickness.
- The cathode is mounted on a water-cooled cathode holder, which is installed in a vacuum chamber of the apparatus. After the vacuum chamber is evacuated to 5 x 10⁻⁶ torr, the high vacuum diffusion pump is throttled, and argon and a reactive gas, or reactive gas alone is admitted to the chamber at a flow rate sufficient to maintain 10 - 20 millitorr pressure in the chamber. Typically the gas flow rates are adjusted throughout a run in order to maintain a constant pressure. An arc is ignited on the cathode surface and is regulated by a constant current power supply to 150 amps for 400 gram abrasive grain charge runs, and 180 amps for 2000 gram charge runs. A solenoid providing a magnetic field of about 50 Gauss serves to duct the titanium or zirconium plasma to the abrasive grain while agitating the abrasive grain in a cylinder fitted with baffles which stir the grain during the coating process. A typical coating run time is about 5 hours.
- In order to test the coated abrasive grain for improved performance, the grain is first conventionally coated on a backing and then converted into 7.6 cm x 335 cm grinding belts. Grinding tests are carried out on a constant load surface grinder. A preweighed mild steel workpiece approximately 2.5 x 5 x 18 cm, mounted in a holder, is positioned vertically, with its 2.5 x 18 cm face confronting an approximately 36 cm diameter 85 Shore A durometer serrated rubber contact wheel with one on one lands over which is entrained the coated abrasive belt. The workpiece is then reciprocated vertically through an 18 cm path at the rate of 20 cycles per minute, while a spring loaded plunger urges the workpiece against the belt under a load of 11.36 Kg as the belt is driven at about 2050 meters per minute.
- The test is run by grinding the preweighed workpiece for 1 minute, reweighing the workpiece to obtain the weight of metal removed, and then cooling the workpiece. Successive workpieces were treated the same way until the workpiece set has been completed and then the cycle is repeated until the desired endpoint is obtained. The amount of stock removed is calculated by adding the amount of metal removed from each workpiece for each minute of grinding to obtain a total weight of metal removed.
- A sample of a heat treated fused alumina (HTA), Grade 150 (average particle size of about 95 micrometers), available commercially from Treibacker Chemishe Werke Aklungesellschaft, Treibach, Austria, was coated via cathodic arc deposition as described above with titanium carbide under the following conditions:
Abrasive Grain Charge Weight: 400 grams Chamber Pressure and atmosphere: 15 millitorr of methane Cathode Current: 150 amps - The grit was exposed to the coating flux for 5 hours, sufficient to yield a coating thickness of approximately 10 nanometers, as calculated. The average coating thickness was calculated from the weight percent of the coating (as determined by standard analytical chemistry methods), the average surface area of the abrasive grain, and the density of the coating material (e.g., titanium nitride has a density of 5.22 g/cc) using the following equation:
where - t =
- the coating thickness
- W =
- weight percent of coating
- D =
- density in g/cc
- S =
- surface area in m²/gram.
- The coated abrasive grain was made into a coated abrasive product using conventional techniques. The coated abrasive product was converted into abrasive belts. Uncoated HTA was used to make a control coated abrasive which was also converted to an abrasive belt.
- In each case the backing material was a Y weight sateen polyester and the belt size was 7.6 cm x 335.3 cm. The backing was coated with a traditional CaC0₃ filled phenol formaldehyde resole resin make coat which, upon curing, contained 45.2% CaC0₃ and 54.8% resin. Then abrasive mineral was applied by electrostatic deposition. The make coat was precured for 2 hours at 80°C and then a size coat was applied. The size coat was a traditional CaC0₃ filled phenolic resole resin which, upon curing, contained 59.6% CaC0₃ and 40.4% resin. After application of the size coat coated abrasive was cured for 12 hours at 100°C.
- The belts were tested on the surface grinder described above by grinding 4 workpieces of 4150 mild steel for a total of 20 minutes at 11.36 Kg pressure. The control was prepared and tested in an identical manner, and results are as follows:
Total Amount of Metal Removed by Control Belt: 352.3 grams Total Amount of Metal Removed by Example 1 Belt: 382.96 grams Percent Improvement: 8.7% - A sample of the heat treated fused alumina (HTA), described in Example 1 was coated via cathodic arc deposition with titanium nitride under the following conditions:
Abrasive Grain Charge Weight: 400 grams Chamber Pressure and Atmosphere: 15 millitorr of nitrogen Cathode Current: 150 amps - The abrasive grain was exposed to the coating flux for 5 hours, sufficient to yield a coating thickness of approximately 10 nanometers. The resulting coated abrasive grain was used to make coated abrasives which were converted into belts and tested as described in Example 1, with results as follows:
Total Amount of Metal Removed by Control Belt: 352.3 grams Total Amount of Metal Removed by Example 2 Belt: 390.6 grams Percent Improvement: 10.8% - A sample of a ceramic sol gel alumina-based abrasive grain, Grade 150, made according to Example 18 (except including 0.5% magnesia) of U.S. Patent No. 4,964,883, was coated via cathodic arc deposition with titanium nitride under the following conditions:
Abrasive Grain Charge Weight: 400 grams Chamber Pressure and Atmosphere: 15 millitorr of nitrogen Cathode Current: 150 amps - The abrasive was exposed to the coating flux for 5 hours, sufficient to yield a calculated coating thickness of approximately 10 nanometers. The resulting coated abrasive grain was used to make coated abrasive product which was converted into abrasive belts and tested as described in Example 1, with results as follows:
Total Amount of Metal Removed by Control Belt: 248.3 grams Total Amount of Metal Removed by Example 3 Belt: 268.26 grams Percent Improvement: 8.2% - Alpha alumina, magnesia-modified, iron oxide-seeded, ceramic abrasive grain obtained under the trade designation "Cubitron" from Minnesota Mining and Manufacturing Company, Grade 150, was coated with zirconium carbide via cathodic arc deposition under the following conditions:
Abrasive Grain Charge Weight: 2000 grams Chamber Pressure and Atmosphere: 15 millitorr of methane Cathode Current: 180 amps - The abrasive grain was exposed to the coating flux for 5 hours, sufficient to yield a calculated coating thickness of approximately 10 nanometers.
- The resulting coated abrasive grain was used to make coated abrasive using conventional techniques and the coated abrasive was converted into abrasive belts. Uncoated Cubitron grain was used to make coated abrasive which was converted to a control belt.
- The coated abrasive backing material was a treated cotton J weight drill cloth, obtained from Gustav Ernstmeier Gmbh and Co. KG, West Germany, and the belt size was 7.6 cm x 335.3 cm.
- The cloth was coated with a traditional CaC0₃ filled phenolic resole resin which, upon curing, resulted in a solids content of 42% CaC0₃ and 58% resin. Then abrasive mineral was applied by electrostatic deposition to a density of 0.0151 gram/cm².
- The make coat was precured according to the following heating schedule:
4 minutes @ 71°C 20 minutes @ 96°C 74 minutes @ 104°C - The size coat was a traditional CaC0₃ filled phenolic resole resin which, upon curing, had a solids content of 80% CaC0₃ and 20% resin. After coating, the belt was cured according the following heating schedule:
20 minutes @ 57°C 40 minutes @ 71°C 20 minutes @ 81°C 80 minutes @ 89°C 90 minutes @ 58°C - Then for a final cure the belt was rolled into a drum and cured for 12 hours at 99°C. The belts were tested on the surface grinder described above by grinding 4 workpieces of 4150 mild steel for a total of 20 minutes at 4.5 Kg pressure with the following results:
Total Metal Removed by Control Belt: 346.46 grams Total Metal Removed by Example 4 Belt: 427.86 grams Percent Improvement: 23.5% - The Cubitron abrasive grain described in Example 4, Grade 150, was coated with zirconium carbide via cathodic arc deposition under the following conditions:
Abrasive Grain Charge Weight: 2000 grams Chamber Pressure and Atmosphere: 15 millitorr of methane Cathode Current: 180 amps - The grit was exposed to the coating flux for 5 hours, sufficient to yield a calculated coating thickness of approximately 10 nanometers. The coated abrasive grain was used to make coated abrasive product which was converted into abrasive belts and tested as described in Example 4, with results as follows:
Total Metal Removed by Control Belt: 304.9 grams Total Metal Removed by Example 5 Belt: 395.1 grams Percent Improvement: 29.6% - While this invention has been described in terms of specific embodiments, it should be understood that it is capable of further modifications. The claims are intended to cover those variations which one skilled in the art would recognize as the chemical equivalent of what has been described here.
Claims (10)
- Abrasive particles, each particle of which is characterized by being an alumina-based core coated with a substantially uniform layer refractory material at an average coating thickness of less than 100 nm, said refractory material being a metal boride, carbide, or nitride.
- The abrasive particles of claim 1 further characterized by said refractory material being a boride, carbide or nitride of a metal selected from the group consisting of scandium, lanthanum, cerium, neodymium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten and mixtures thereof.
- The abrasive particles of claim 1 further characterized by said coating thickness being greater than about 1 nm.
- The abrasive particles of claim 1 further characterized by said coating thickness being 5 to 25 nm.
- An abrasive article in the form of a coated abrasive product, a bonded abrasive product or a nonwoven abrasive product comprising abrasive particles characterized by at least a portion of said abrasive particles being the abrasive particles of claim 1.
- A process for making abrasive particles, said process characterized bya) applying sufficient current to a metal cathode to form a plasma of the metal comprising the cathode;b) subjecting said plasma to an atmosphere conducive to the formation of the boride, carbide or nitride of the metal of said plasma;c) permitting said plasma to be directed in a path through an anode;d) maintaining alumina-based particles to be coated within said path;e) rotating each alumina-based particle to substantially expose the entire surface of each of said particles to said plasma path;f) continuing steps a-e until a substantially uniform coating of refractory material is coated on substantially every alumina-based particle, andg) discontinuing steps a-f before the average coating thickness of refractory material on the alumina-based particles exceeds 100 nm.
- The process of claim 6 further characterized by said atmosphere comprising an inert gas.
- The process of claim 7 further characterized by said inert gas being selected from argon, krypton, xenon, helium, or a member of Group 8 of the Periodic Table.
- The process of claim 6 further characterized by said atmosphere comprising a reactive gas.
- The process of claim 9 further characterized by said reactive gas comprising oxygen, nitrogen, ammonia, a hydrocarbon or a boron-containing gas.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US517931 | 1990-05-02 | ||
US07/517,931 US5085671A (en) | 1990-05-02 | 1990-05-02 | Method of coating alumina particles with refractory material, abrasive particles made by the method and abrasive products containing the same |
PCT/US1991/002035 WO1991017225A1 (en) | 1990-05-02 | 1991-03-26 | Coated abrasive alumina particles, manufacture and use |
Publications (2)
Publication Number | Publication Date |
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EP0527143A1 EP0527143A1 (en) | 1993-02-17 |
EP0527143B1 true EP0527143B1 (en) | 1994-09-14 |
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Application Number | Title | Priority Date | Filing Date |
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EP91907376A Expired - Lifetime EP0527143B1 (en) | 1990-05-02 | 1991-03-26 | Coated abrasive alumina particles, manufacture and use |
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US (2) | US5085671A (en) |
EP (1) | EP0527143B1 (en) |
JP (1) | JPH05506678A (en) |
KR (1) | KR0179636B1 (en) |
CN (1) | CN1027239C (en) |
AT (1) | ATE111501T1 (en) |
AU (1) | AU639555B2 (en) |
BR (1) | BR9106401A (en) |
CA (1) | CA2080598A1 (en) |
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MX (1) | MX167416B (en) |
NO (1) | NO924189L (en) |
RU (1) | RU2092514C1 (en) |
TW (1) | TW201789B (en) |
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1990
- 1990-05-02 US US07/517,931 patent/US5085671A/en not_active Expired - Fee Related
-
1991
- 1991-03-26 EP EP91907376A patent/EP0527143B1/en not_active Expired - Lifetime
- 1991-03-26 BR BR919106401A patent/BR9106401A/en not_active IP Right Cessation
- 1991-03-26 AT AT91907376T patent/ATE111501T1/en not_active IP Right Cessation
- 1991-03-26 WO PCT/US1991/002035 patent/WO1991017225A1/en active IP Right Grant
- 1991-03-26 DE DE69104039T patent/DE69104039T2/en not_active Expired - Fee Related
- 1991-03-26 RU RU9192016414A patent/RU2092514C1/en active
- 1991-03-26 AU AU75533/91A patent/AU639555B2/en not_active Ceased
- 1991-03-26 KR KR1019920702727A patent/KR0179636B1/en not_active IP Right Cessation
- 1991-03-26 JP JP91506665A patent/JPH05506678A/en active Pending
- 1991-03-26 CA CA002080598A patent/CA2080598A1/en not_active Abandoned
- 1991-04-10 TW TW080102730A patent/TW201789B/zh active
- 1991-04-12 ZA ZA912765A patent/ZA912765B/en unknown
- 1991-04-23 MX MX025479A patent/MX167416B/en unknown
- 1991-04-30 CN CN91102779A patent/CN1027239C/en not_active Expired - Fee Related
-
1992
- 1992-01-31 US US07/828,514 patent/US5163975A/en not_active Expired - Lifetime
- 1992-10-30 NO NO92924189A patent/NO924189L/en unknown
Also Published As
Publication number | Publication date |
---|---|
DE69104039T2 (en) | 1995-03-30 |
CN1027239C (en) | 1995-01-04 |
WO1991017225A1 (en) | 1991-11-14 |
NO924189D0 (en) | 1992-10-30 |
RU2092514C1 (en) | 1997-10-10 |
BR9106401A (en) | 1993-05-04 |
CA2080598A1 (en) | 1991-11-03 |
MX167416B (en) | 1993-03-22 |
KR0179636B1 (en) | 1999-05-01 |
DE69104039D1 (en) | 1994-10-20 |
EP0527143A1 (en) | 1993-02-17 |
AU639555B2 (en) | 1993-07-29 |
ATE111501T1 (en) | 1994-09-15 |
AU7553391A (en) | 1991-11-27 |
NO924189L (en) | 1992-12-30 |
ZA912765B (en) | 1992-01-29 |
TW201789B (en) | 1993-03-11 |
CN1056078A (en) | 1991-11-13 |
US5163975A (en) | 1992-11-17 |
JPH05506678A (en) | 1993-09-30 |
US5085671A (en) | 1992-02-04 |
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